NOTES
2812
VOl. TO
TABLE I AXXINATIVE HYDROGENATION O F KETONES' Wt., g.
Carbonyl compound
NHa Moles
sol.,b
cc.
Cat..c
g.
Product
B. P.,
Yield,
%
OC.
Mm.
---Yo
Calcd.
NFound
118 Phenylacetoned 0.89 400 22 CoHiaN' 85 80 10 10.4 10.1 29.2 .21 Benzalacetone' 400 5 CioHiiN' 67 80 4 9.4 9.4 100 Furfuralacetone* .74 300 7 G H ~ ~ O N 50 ~ 190 760' 10.0 10.3 130 (I) .67 400 B-Ionone' 5 CiaHsN' 93 78 0.3" 7.2 7.2 25.4 .20 100 Diethylamino5 C,HiaNso 65 154 76OP acetone" 14.3 4-Diethylamino-2.10 100 1.5 CSHmNz' 72 70 10 butanoneq 15.7 5-Diethylamino-2.10 150 15 CoHlnNz' 85 196-198 755 17.8 17.9 pentanone a Hydrogen pressure a t 1 atm. or slightly above; temperature a t 20'or slightly above. 17% NHa in ethanol. Raney nickel. "Organic Syntheses," Coll. Vol. 11, p. 487; Bobranskii and Drabik, C. A . , 36,2531 (1942). a Hydrochloride, m. p. 146'. By-product: 10.2 g. (8%) bis-(l-phenylpropyl-2)-amine,CleHsN, b. p. 154" (2mm.). Calcd.: N, 5.5. Found: N, 5.5. f B. p. 153" (25mm.). 0 Previously prepared by reduction of the oxime (Harries and de Osa, Ber., 36, 2999 (1903); Bargellini, Beilstein, 12, 1165) or phenylhydrazone [Schlenk, J . prakt. Chem.,78, 57 (1908)]of benzalacetone. Hydrochloride, from ethyl acetate, m. p. 148'. * Leuck and Cejka, "Organic Syntheses," Coll. Vol. I, p. 283. See also Chem. Zentr., 103,II, 2183 (1932). s% 1.4730. Calcd.: C, 69.0; H, 9.3; mol. wt., 139. Found: C, 68.5;H, 9.4; mol. wt., 142. By-product, 18 g. (19%) of di-(l-a-furylbutyl-3)-amine, CldfnO~N,b. p. 128' (0.05 nim.), nZgD1.4942. Calcd: C, 73.5; H,8.8; N, 5.4. Found: C, 74.0; H, 8.3; N, 5.0. i B. p. 102" (25mm.). E B. p. 100102' (2 mm.). nZ7D1.4800. Calcd.: C, 80.0; H, 12.8; mol. wt., 195. Found: C, 79.9; H, 12.6; mol. wt., 185. Hydrochloride, m. p. 212', very soluble in water; chloroplatinate, m. p. 216' (dec.); picrate (from 60% ethanol), m. B. p. 115' (30 mm.). Stoermer and Dzimski, Ber., 28,2220 (1895). By-product, 1.4 g. of bh(3-diethylp. 176'. aminopropyl)-2-amine, CIdHBSN8,b.p. 150' (20mm.). Calcd.: N,17.3. Found: N,17.3. p B. p. 70' (20mm.). * Mannich, Arch. Pharm., 255,261 (1917);Soh1 and Shnner, THISJOURNAL, 55,3828 (1933); Emerson, ibid., 60,2023 (1938); 65,471 (1943);du Feu, McQuillin and Robinson, J . Chem. SOL, 56 (1937); Tuda, Hukusima and Oguri, C. A., 36,3154 (1942). Yield, 60%, b. p. SO' (18mm.), n t e 1.463, ~ dZ4d0.863. dz0z00.826; 1.4430. By-product, 1.1 g. of bis-(4diethylaminobutyl-2)-amine,CleHarN3, b. p. 152-155' (22 mm.). Calcd.: N, 15.5. Found: N, 15.5. ,. dzod0.8296, n% 1.4442. Calcd.: C, 68.3; H, 13.9. Found: C, 68.0; H, 14.0. Chloroaurate, m. p. 157",lit. 155'. By-product, small amount of bis-(5-diethylaminopenty1-2)-amine,C1&N3, b. p. 152' (3mm.). Calcd.: N, 14.0. Found: N,14.6. No exact proof of formula (11), however, has so far been obtained.
x,
CHa CHs CH=CHCOCH,
\'CHa
CHa CHa X/CH*CH&HCHa 1
I CHI CHs CHzCHzCHCHa
I
OH &!Ha
2-aminobutane and 3-diethylamino-2-aminopropane, respectively. I n each of the three cases, a higher-boiling by-product was observed in small quantities, which analyzed for the corresponding secondary amine [ (CzH&N(CHz),CH(CHa)]?NH.. For n = 3, the structure was proved by conversion into 5-diethylamino-2-aminopentaneaccording to Grigorowski, Margolina and Magidson' with 4Oy0 yield. Assignment of the analogous structures in the other two cases appears justified. (7) Grigorowski, Margolioa and Magidson, ibid., 109, (1938).
II, 768
WEIZMANN INSTITUTE OF SCIENCE DANIELSIEFFRESEARCH INSTITUTE REHOVOTH, ISRAEL RECEIVED JANUARY 2, 1947
I11
Reaction of Benzyl Bromide with Ethyl The amines of the general formula ( C S H ~ ) ~ N ( C H S )The ~CH(NH,)CH* are usually prepared by reduction of the a-Acetoxyacetoacetate corresponding ketoximes.' It has been found that they BY NATHAN GREENAND F. B. LAFORGE can be obtained directly from the ketones by catalytic hydrogenation in presence of ammonia under fairly mild conDimroth and Schweitzer' have described the ditions.5 In the case of 5-diethylamino-2-aminopentane (from 5-diethylamin0-2-pentanone)~ the product was char- preparation of ethyl a-acetoxyacetoacetate and acterized by its known8 chloroaurate; it is believed that state that the sodium derivative reacts with halothe products obtained from 4diethylamino-2-butanone and diethylaminoacetone are, analogously, 4-diethylamino- gen compounds, giving substitution products.
The resulting compounds were not further investigated, however. The present investigation is a study of the reaction of benzyl bromide with the sodium derivative of ethyl a-acetoxyacetoacetate, and of the behavior of the product. (5) Breslow, Walker, Yost, Shivers and Hauser [THISJOURNAL, The reaction with benzyl bromide proceeded 68, 100 (1946) I carried out this reaction under high pressure. normally, giving ethyl a-acetoxy-a-benzylaceto(6) Knunjanz, Toptschijew and Tschelinzew, Chum. Zanfr., 106, (4) (a) Magidson and Grigorowsky, Bur., 69, 401 (1936); (b) Magidson, Grigorovsky, Melnikov and Klein, Prom. &E. K h i m j i , 596 (1938) ; Knunyantz, Chelintzev and Osetroua Russian Patent 35,837 [C. A . . P9, 8007 (1936)); Grigorowki Russian Patent 48,203 [Cham. Zcntr., 108, 11, 472 (1937)J; (c) Breslow. cf. al., THIS JOURNAL, 66, 1921 (1944).
I, 1896 (1985).
(1) Dimrnth and Schwdtrer, Ber., 66, 1381 (1923).
Aug., 1948 acetate. An acetyl determination on the product showed two acetyl groups. Attempted ketone cleavage with sodium ethylate, or even with cold dilute aqueous barium hydroxide, removed two acetyl groups and gave 8-phenyllactic acid as the end-product. The reaction had therefore proceeded exclusively in the sense of the acid cleavage with simultaneous saponification of the acetoxy group. Attempts at acid hydrolysis were also unsuccessful, where the compound showed great resistance to t h i s treatment. It is probable that the reaction of halides with a-acetoxyacetoacetates may be generally useful in the preparation of a-hydroxy acids. Experimental Part Ethyl a-Acetoxyacetoacetate.LEighty-four grams of
NOTES
2813
zene. The product nielted at 95-90", neutralization equivalent 166, and was identified as 6-phenyllactic acid.a Hydrolysis with Barium Hydroxide.-Five and onehalf grams of ethyl a-acetoxy-a-benzylacetoacetatewas added to 250 ml. of a 2.5% aqueous solution of barium hydroxide, and the suspesision was shaken for forty-eight hours. Carbon dioxide was then passed into the solution to remove the excess alkali. After the barium carbonate had been filtered off, most of the water was removed under reduced pressure. On addition of ethanol, 5.8 g. of crude barium salt of 8-phenyllactic acid was obtained. (2) Ber., 43 [4], 4892 (1908).
U. S. DEPARTMENT OF AGRICULTURE AGRICULTURAL RESEARCH ADMJNISTRATION BUREAU OF ENTOMOLOGY AND PLANT QUARANTINE RECEIVEDMAY17, 1948 BELTSVILLE, MARYLAND
Preparation of 1,Z-Dichloropropene-1 ethyl acetoacetate (0.65 mole) was dissolved in 320 ml. of benzene, and 88 g. of lead tetraacetate (0.6 mole calcuBY ERNESTH. HUNTRESS AND F. SANCHEZ-NIEVAI Fated on a 100% basis) was added in several small pytions with stirring, the temperature being kept below 35 . The In view of the extent of recent studies of chloromixture was stirred for one-half hour after the last addition, and then ice-water was added and the layers were and polychloro-olefins the paucity of reports on separated. The benzene solution was washed with ice 1,2-dichloropropene is remarkable. This comwater and sodium bicarbonate solution, dried, and dis- pound should exist in two geometrically stereoisotilled from a modified Claisen flask. Forty-one grams meric forms. The only record of the lower boiling (34%) of product was obtained boiling a t 125-127 O a t 17.5 stereomer is an ancient report2 claiming its prepmm., n * 6 ~ 1.4280. The compound distills as a pale yellow liquid, which aration from 1,2,2-trichloropropane by dehydrobecomes colorless upon standing. It readily reduces chlorination with alcoholic potassium hydroxide. Fehling solution in the cold. Anal. Calcd. for CsHlzOs: A liquid regarded as the higher boiling stereomer GHsO, 23.9. Found: QH60.23.8. Ethyl a-Acetoxya-benzy1acetoacetate.-Two and four- was subsequently obtained3 from a,8,B-trichlorotenths grams (0.1 mole) of sodium hydride was placed in a n-butyric acid by solution and heating in aqueous nitrogen-swept flask with 100 ml. of dioxane, and 18.8 g. sodium carbonate. None of the cited papers give (0.1 mole) of the acetoxy compound in 40 ml. dioxane was satisfactory details. added dropwise to the stirred mixture over a period of We have developed the preparation of the lower thirty minutes. After an additional thirty minutes 17.1 g. (0.1 mole) of benzyl bromide was added slowly, and the boiling stereomer to give readily 5538% yields, mixture was then refluxed for one and a half hours. The have established certain needed physical conreaction mixture was poured into 1 liter of water contain- stants, have shown that upon ozonolysis the ing sufficient acetic acid t o neutralize the alkali. The heavy oil which separated was extracted twice with ether, compound yields formic and acetic acids, and that and the ethereal solution was washed with water and then with methanol it gives an azeotrope. We did nst, with saturated sodium chloride solution. The solution in this work, study the preparation of the supwas dried, the solvent removed, and the product distilled posed higher boiling stereomer3but all attempts to from a modified Claisen flask. The yield was 18.6 g. isomerize the lower boiling material were unsuc(67%) of product boiling at 118-122' a t 0.5 mm., +D cessful. The configuration of the two stereomers 1.4916. Anal. Calcd. for C16H1s06:C, 64.73; H, 6.52; CaH60, is still undetermined. 16.2; 2CHaC0, 30.9. Found: C, 64.02; 13, 6.72; 1,2-Dichloropropene-l ( h e r boiling stereomer) .--One CsHsO, 16.0; CHnCO, 26.7. mole of 1,2,2-trichloropropane (b. p. 123-125' at 762.4 Hydrolysis of Ethyl a-Acetoxyiu-benzy1acetoacetate.~ obtained from 2-chloropropene-1 by mm., d 6 1.4609, The compound was unchanged by refluxing with water addition of chlorine) was added dropwise with frequent for one hour. Refluxing with glacial acetic acid containing shaking to a 25% solution of sodium methoxide (1.3-1.5 a little concentrated hydrochloric acid also failed to hy- moles) in methanol kept cold in ice water. After comdrolyze the compound. Although some carbon dioxide pletion of the vigorous reaction the solution was poured was evolved by the process, the starting material was re- into a large volume of water, and the heavy insolubre covered almost quantitatively. The same was true when layer washed, dried and distilled. Because of its much the compound was refluxed with 2070 sulfuric acid. The higher boiling point any unreacted trichloropropane was products of these experiments were identified, by boiling easily separated from the desired dichloropropene (55-5875 points, refractive indices and ethoxyl analyses, as the origi- yield). nal material. Redistillation of the crude product through a ten Hydrolysis with Sodium Ethylate .-Five and one-half theoretical plate column gave the lower boiling 1,2-digrams (0.02 mole) of ethyl cr-acetoxy~a-benzylacetoace- chloropropene-1, b. p. 76.8-77.0' a t 757.0 mm.; des, tate was added to 2 g. of sodium dissolved in 35 ml. of 1.1755, dmi 1.1818, n"D 1.4451, nmD 1.4471. ethanol and the solution was refluxed for one hour. Most This product formed with anhydrous methanol an azeoof the alcohol was removed under diminished pressure, (1) From part of a t%esis submitted by Mr. Sanchez-Nieva in and the residue was acidified to congo red with dilute hydrochloric acid. The solution was then saturated with October, 1945. in partial fuliiIIment o! the requirementsfor the degree sodium chloride and extracted several times with ether. of Master of Science at M.I. T. (2) Priedel and Silva, Comgt. rend., 74,807 (1872); 76, 81 (1872); On evaporation of the solvent on the steam-bath and subBull. soc. chim., [21 ll, 886 (1872); Johresbn., 322, 329 (1871). sequently under reduced pressure, 3.3 g. of crystalline (3) Srenic and Taggeeell, Be?., LE, 2667-2668 (1895). material was obtained, which was recrystallized from ben-
